Textile softening compositions

ABSTRACT

A method and composition for simultaneously cleansing and softening textiles without yellowing by utilizing a detergent composition containing effective amounts of an alkylated polyethyleneimine polymer, the ratio of detergent to polymer ranging from 20:1 to 1:5 and preferably 10:1 to 1:2.

United States Patent Gerecht et al.

[4 1 July 11, 1972 [54] TEXTILE SOFTENING COMPOSITIONS [72] Inventors: John Fred Gerecht, Somerville; Harold Eugene Wixon, New Brunswick, both of NJ.

[73] Assignee: Colgate-Palmolive Company, New York,

[22] Filed: March 15, 1971 [21] Appl. No.: 124,515

Related US. Application Data [63] Continuation-in-part of Ser. No. 733,316, May 31,

1968, abandoned.

[52] US. Cl .1 ..252/8.8, ll7/139.5 CQ, 252/8.75, 252/525, 252/527, 252/544, 252/546 [51] lnt.Cl. ..Cl1d3/04,C1 1d1/38 [58] Field ofSearch ..252/8.75, 8.8, 525, 544; ll7/139.5 CQ

Primal Examiner-Herbert B. Guynn Attorney-Herbert S. Sylvester, Murray M. Grill, Norman Blumenkopf, Ronald S. Cornell, Thomas J. Corum, Richard N. Miller, Robert L. Stone and Kenneth A. Koch 1 1 ABSIRACT A method and composition for simultaneously cleansing and softening textiles without yellowing by utilizing a detergent composition containing effective amounts of an alkylated V polyethyleneimine polymer, the ratio of detergent to polymer ranging from 20:1 to 1:5 and preferably 10:1 to 1:2.

6 Claims, No Drawings TEXTILE SOFTENING COMPOSITIONS This application is a continuation-in-part of Ser. No. 733,316, filed May 31, 1968, now abandoned.

The present invention relates to a non-yellowing textile softening composition containing an alkylated polyethyleneimine polymer which is compatible with an anionic detergent and/or a nonionic detergent.

Softening agents have been used in laundering in order to render fabrics or textiles soft, and the term softening refers to the handle, hand, touch or feel; this is the tactile impression given by textiles to the hand or body and is of aesthetic and commercial importance. Softening realized with such agents varies with a number of factors including: laundry load weight and composition, types of bleach used if any, detergents used, the initial degree of harshness, type of washing machine, water temperature, etc. The most commonly used softening agents are cationic, such as the quaternary ammonium compounds because of their particular effectiveness. However, aforesaid compounds have the serious disadvantage of causing fabric yellowing which is caused by the deposition of yellow color bodies from the rinse water onto the fabric. Color imparted to textileslaundered with cationic softening agents have been found to be related to the amount of softening given to the textiles. That is, with highly colored water supplies, laundered textiles have a greater degree of yellowness or yellow color when a substantial and effective amount of softening agent is used herewith.

In addition to the aforedescribed yellowing problem, the prior art quaternary softening agents are incompatible with anionic detergents commonly used in laundering because of reaction or interaction therewith, thereby depleting the detergency action in the washing operation as well as forming precipitates which deposit on the washed articles, giving them an undesirable appearance. Consequently, fabric-softening applications have necessarily been conducted separately such as after the washing operation, preferably during the rinsing cycle in the laundering of fabrics.

Accordingly, it is an object of this invention to provide compositions capable of simultaneously cleansing and softening fabrics with a minimal, if any, yellowing normally associated with fabric softening.

It has now been found that acomposition capable of both cleansing and softening textiles without yellowing in a single operation comprises an anionic and/or non-ionic detergent and (an effective amount of) an alkylated polyethyleneimine polymer in a ratio of 20:1 to 1:5.

The alkylated polyethyleneimine polymers contemplated by this invention as softening agents are solid, water dispersible or water soluble partially alkylated polythyleneimine polymers free of inorganic salts. The molecular weight of the polymer can vary over a wide range inclusive of 1,000 to 100,000, but a preferred group of polymers have a molecular weight of 40,000 to 75,000. It is essential that the polyethyleneimine be only partially alkylated since a completely alkylated polymer is inoperative herein. The optimum degree of alkylation is 5 50 percent with l0 40 percent being preferred. This can be accomplished by reacting 0.05 mole equivalent to 0.5 mole and preferably 0.1 0.4 mole of an alkylating agent per mole of ethyleneimine monomer. The alkylating agent is an alkyl halide or sulfate containing from 16 to 30 carbon atoms per mole equivalent and preferably'l 22 carbon atoms. Examples of suitable alkylating agents include octadecyl bromide, octadecyl chloride, heptadecyl chloride, hexadecyl bromide, hexadecyl sulfate, eicosyl chloride, tricosyl bromide, etc.

The partially alkylated polyethyleneimine polymers are prepared in any suitable manner. A preferred method constitutes reacting the polyethyleneimine polymer with less than the stoichiometric amount of an alkylation agent, such as an alkyl halide, in the presence of a solvent, under reflux conditions, for a sufficient period of time to effect complete reaction therebetween. Partial alkylation preserves the presence of some nitrogen-bonded hydrogens present in the polymer molecules, since the alkyl radicals replace the hydrogen atoms attached to the nitrogen atoms.

Completion of the reaction is indicated by the cessation of the formation of hydrogen halide and can vary from about 2 hours to about 8 hours. The solvent may be an alcohol such as methyl, ethyl, propyl, isopropyl and butyl alcohol. The amount of solvent is not critical. The reaction mixture is freed of the solvent by evaporation, distillation or the like. The residue is purified by dissolution in a hydrocarbon solvent such as benzene, toluene or xylene and treated with an alkaline solution such as sodium hydroxide, sodium methylate, etc., to eliminate the hydrogen halide and obtain the free base, which is recovered by freeze drying or vacuum drying as indicated. The procedural steps in the purification and recovery of the alkylated polymer are not critical. Variations in purification techniques are available, depending, inter alia, upon the degree of alkylation. The greater the degree of alkylation the less soluble is the resultant product in polar solvents, e.g., water, alcohol and water-alcohol mixtures. The alkaline solution, i.e., sodium methylate, may be added directly to the reflux solution at the completion of the alkylation process to convert the polymer to the free base and precipitate out the sodium halide salt. The solvent is removed from the reaction mixture via distillation, evaporation or by other suitable means and the residue purified in benzene or the like and subsequently dried. Another variation in the recovery of the polymer involves the acidification of the reaction mixture with acetic acid, hydrochloric acid, hydrobromic acid, etc., in an aqueous medium in lieu of the alkalizing step with the aqueous suspension of partially alkylated polyethyleneimine being used as such. However, the preferred method of obtaining purified samples of the partially alkylated polyethyleneimine polymers after alkylation comprises treating with 10 percent excess of sodium, methylate to liberate the free base. The alcohol is then distilled off, the polymer taken up in benzene, and any water removed by codistillation. The insoluble sodium bromide is filtered off, and the benzene solution slowly poured into methanol to precipitate the polymer. Polymers containing 0.25, 0.30 and 0.40 equivalents of .octadecyl groups per monomer unit are obtained from a polymer of molecular weight 4060,000. However, the polymer containing 0.20 equivalents or less of octadecyl groups can not be precipitated in this way, and is recoverable by freeze drying the benzene solution.

The following examples illustrate the partial alkylation of the polyethyleneimine polymer:

EXAMPLE l 13 grams of a 33 percent aqueous solution of polyethyleneimine of molecular weight 40,000 60,000 containing 4.3 gms. of anhydrous polymer are dissolved in 75 ml of ethyl alcohol and l0 gms. of octadecyl bromide, which is equivalent to 0.3 mole per monomer unit, are added to the clear solution. A two phase mixture is formed which is refluxed for 4 hours. The reaction mixture gradually becomes homogeneous and then the polymer which is approximately 30 percent alkylated precipitates out of solution. The reaction mixture is heated on a steam bath to remove most of the alcohol. The residue is suspended in water and the pH is adjusted to 4.5 with acetic acid, which converts the product at least partially to the salt, and the aqueous suspension of partially alkylated polyethyleneimine is used as such.

EXAMPLE ll 13 gms. of a 33 percent aqueous solution of polyethyleneimine polymer having a molecular weight of 40,000 60,000 containing 4.3 gms anhydrous polymer are reacted with 8.3 gms. of l-bromooctadecane which is equivalent to 0.25 mole per monomer unit in the presence of mo ml. of ethanol by refluxing for 4 hours. An insoluble white polymer to the free base. After standing awhile, most of the alcohol is distilled off and about 200 ml. benzene is added to the residue to dissolve it. The water and residual alcohol are removed by filtration. The benzene solution is poured into 500 ml. of methyl alcohol to precipitate the alkylated polymer which is allowed to settle, the solvent decanted from the solid and collected on a filter. The residue is washed and dried in vacuum and found to be substantially free of halogen.

EXAMPLE III A partially alkylated polymer is prepared in accordance with Example 1, except that the substantially alcohol-free residue is dissolved in about 150 ml of benzene to which is added 6 ml of 5.1 N methyl alcoholic caustic to convert the polymer to the free base. To isolate the free base, the water and benzene are codistilled. After the water is removed, the remaining benzene solution is filtered to remove salts and the clear filtrate is freeze-dried to recover the polymer.

EXAMPLE [V 39.0 gms. of a 33 percent aqueous solution of polyethyleneimine having a molecular weight of 50,000 100,000 are reacted with 20.0 gms. of l-bromooctadecane, which is equivalent to 0.2 moles per monomer unit, in the presence of 225 ml. of ethanol by refluxing for 3 hours. 11.7 ml. of 5.12 N sodium hydroxide in methyl alcohol is added to liberate the free base and the bulk of the solvent is removed on a steam bath. Benzene is added to the residue and all the water and alcohol is codistilled off. The resulting solution is filtered to remove the sodium bromide and the clear benzene filtrate is freeze-dried to recover the polymer as a white powder.

The partially alkylated polyethyleneimine polymers are valuable softening agents for textiles and fabrics manufactured from synthetic and natural fibers and blends thereof, inclusive of cellulose, dacron-cotton blend, nylon, wool, cotton, orlon blends and the like. These polymers are stable, watersoluble and/or water-dispersible compounds, capable of imparting the desired degree of softness with a minimal, if any yellowing, when utilized in amounts of 0.05 1 percent and preferably 0.1 0.5 percent by weight of the fabric. The fabric treated with the softening agent is impregnated and coated therewith via the transferrance of the agent from the aqueous medium onto the fabric, the higher dosages being retained on the treated fabrics even after several subsequent washings without treatment to yield a soft, fluffy fabric. Laboratory tests have shown fabrics treated in accordance with this invention will not yellow with age or with repeated treatments. Another beneficial characteristic of these softening agents is their compatability with both anionic and nonionic detergents, thereby enabling their conjoint use to simultaneously effect cleansing and softening.

The anionic detergents which may be used in the compositions of this invention include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, phosphonate and phosphate. Examples of suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e. g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about 8 to 26, and preferably about 12 to 22, carbon atoms to the molecule.

As examples of suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of higher alkyl benzene sulfonates or of the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate. In one preferred type of composition there is used a linear alkyl benzene sulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50 percent) of 2- (or lower) phenyl isomers; in

other terminology, the benzene ring is preferably attached in large part at the 3 or higher (e.g. 4,5,6 or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2 or 1 position is correspondingly low. Particularly preferred material are set forth in U.S. Pat. No. 3,320,174, May 16, 1967 of]. Rubinfeld.

Other anionic detergents are the olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkanesulfonates. These olefin sulfonate detergents may be prepared, in kown manner, by the reaction of 50;, with long chain olefins (of 8-25, preferably 12-21 carbon atoms) of the formula RCH=CHR where R is alkyl and R is alkyl or hydrogen, to produce a mixture of sultones and alkenesulfonic acids, which mixture is then treated to convert the sultones to sulfonates. Examples of other sulfate or sulfonate detergents are paraffin sulfonates, such as the reaction products of alpha olefins and bisulfites (e.g. sodium bisulfite), e.g. primary parafiin sulfonates of about 10-20, preferably about 15-20, carbon atoms; sulfates of higher alcohols; salts of sulfofatty esters (e.g. of about 10 to 20 carbon atoms, such as methyl 0:- sulfomyristate or a(e.g.

Examples of sulfates of higher alcohols are sodium lauryl sulfate, sodium tallow alcohol sulfate. Turkey Red Oil or other sulfated oils, or sulfates of monoor diglycerides of fatty acids (e.g. stearic monoglyceride monosulfate), alkyl poly (ethenoxy) ether sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having one to five ethenoxy groups per molecule); lauryl or other higher alkyl glyceryl ether sulfonates; aromatic poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having one to six oxyethylene groups per molecule).

The suitable anionic detergents include also the acyl sarcosinates (e.g. sodium lauroylsarcosinate), the acyl esters (e.g. oleic acid ester) of isethionates, and the acyl N-methyl taurides (e.g. potassium N-methyl laurolyor oleyl-tauride).

The most highly preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates. The particular salt will be suitably selected depending upon the particular formulation and the proportions therein.

in addition to the anionic surface active agents, the instant compositions may contain nonionic agents which include those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group, such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with polymers, e,g., polyethylene glycol.

As examples of nonionic surface active agents which may be used, there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with l0 to 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof, such as sorbitan monolaurate, sorbitol monooleate and mannitan monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide.

The anionic and/or nonionic detergent component may comprise from 1 to percent by weight of the total composition with the balance polymer and any other desirable adjuvants. A preferred range is 5 to 50 percent by weight.

Water-soluble builder salts may also be present, in the usual proportions, in the detergent formulations when heavy duty cleaning is desired. These salts include phosphates and particularly condensed phosphates (e.g. pyrophosphates or tripolyphosphates), silicates, borates and carbonates including bicarbonates), as well as organic builders, such as salts of nitrilotriacetic acid, citric acid, glycollic acid, and methyl vinyl ether-maleic anhydride interpolymers, ethylene diarnine tetraacetic acid. Sodium and potassium salts are preferred. Specific examples are sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium tetraborate, sodium silicate, salts (e.g. Na salt) of methylene diphosphonic acid, trisodium nitrilotriacetate, or mixtures of such builders, including mixtures of pentasodium tripolyphosphate and trisodium nitrilotriacetate, sodium citrate, sodium glycollate, methyl-vinyl ether-maleic anhydride interpolymer (lzl mole ratio, sp. 0.8). The amount of builder may vary from 1 to 100 parts by weight per part of anionic and/or nonionic detergent. A preferred range is l to 50 parts per part of detergent and a most preferred range is 5 to 50 parts by weight per part of anionic and/or nonionic detergent.

Other additives included in the instant deterggent compositions depend on the particular end use and physical form in which is is to be employed. Minor amounts of soil suspending agents, such as carboxymethyl cellulose, cyanoethylated starches and the like may be added. Other additives include optical brighteners, bleaches, germicides, fungicides, bacteriocides, odorants, colorants, etc., in minor amounts which do not interfere with the softening properties of the composition. Where it is desired to formulate a hard surface cleanser, scouring abrasives, such as diatomaceous earth, ground pumice, bentonite and various other clay and clay-like substances, may be included.

The effectiveness of this material as a softening agent for cloth in the presence of detergents and sodium tripolyphosphate was demonstrated in the l-towel test; one terrycloth hand towel washed in a conventional automatic washer, following the regular wash, rinse, and spin dry cycles, and using tap water at 120 F. The treated towels were evaluated for softness and yellowness. Whiteness values are determined with a Gardner Color Difference Meter, using the +b scale as a measure of the yellow chromaticity. However, higher +b values or whiteness numbers indicate a high amount of yellowness and poor results; whereas low +b values or whiteness numbers denote less yellowness or greater whiteness and excellent results. A difference of 0.5 b units in the test represents a difference which is visible to the eye. The softness scale of l to represents no softness at value 1 to excellent softness at value 10. A rating of at least 5 is considered necessary for adequate softening performance.

Softness Rating Yellowness I. 4 gms. dimethyl ditallow ammonium chloride 2. 10 g. sodium tridecyl benzene sulfonate plus 40 gms. sodium tripolyphosphate l 4.7 gms. of the alkylated polyethyleneimine of Example I, containing 0.3 equivalents octadecyl group per monomer unit, plus 40 g. sodium tripolyphosphate 8 4. Composition 3 plus 10 gms. sodium tridecyl benzene sulfonate 9 5. Composition 3 plus 10 gms.

ethoxylated straight chain alcohol containing 14 to 18 carbon atoms (9 ethoxy groups) 7 Polyethyleneimine of 40,000

60,000 molecular weight I Composition of Example 6 plus sodium tri olyphosphate l 4.7 g. 30% alky ated (octadecyl) polyethyleneimine of molecular weight 1,000 5,000 plus 40 g. sodium tripolyphosphate 7 4.4 g. 40% alkylated (octadecyl) polyethyleneimine (M.W. 40,000 tripolyphosphate 7 l0. Composition of Example 9 plus 20 g. sodium tridecyl benzene sulfonate plus I b. sodium carboxy methyl cellulose 5 +1.5

l l. l.7 g. sodium tridecyl benzene sulfonate 1 12. 1.7 g. sodium tridecyl benzene sulfonate plus 1.0 g. alkylated polyethyleneimine of Example [V I3. Composition of Example 12 plus 6.6 gms. sodium tripolyphosphate 14. Composition of Example 12 plus 6.6 gms. sodium nitrilotriacetate l.7 gms. ethoxylated straight chain alcohol containing 14-18 carbon atoms and 9 ethoxy groups (nonionic surfactant) 1 16. 1.7 gms. of the nonionic surfactant of Example 15 plus 1 gm. alkylated polyethyleneimine of Example IV 17. Composition of Example 16 plus 6.6 gms. sodium tripolyphosphate 9 l8. Composition of Example 16 plus 6.6 grns. sodium nitriloacetate The above table clearly shows the superior results obtained with compositions containing the alkylated polyethyleneimine polymer softening agent in the presence of an anionic surfactant (compositions 4, l2, l3, and 14) or a nonionic surfactant (compositions 5, l6, l7, and 18) in the presence or absence of builder salts, wherein the softening action is equivalent to that of the prior an cationic agent (composition 1) but without the objectionable yellowing associated therewith. The dual function of the present formulations is clearly evident by their high softness rating and low yellowness valueas compared to detergent compositions lacking the alkylated polyethyleneimine polymer (compositions 2, 11, and 15). The effectiveness of the alkylated polymer as a softening agent as compared to the total ineffectiveness of the non-alkylated polymer is clearly evident by a comparison of the results against compositions 6 and 7. Furthermore, the cited compositions confirm the effectiveness of a wide range of alkylated polyethyleneimine polymers inclusive of low and high molecular weight polymers, alkylated with 0.1 to 0.5 equivalents of an alkyl group per monomer unit of ethyleneimine.

What is claimed is:

1. A composition effective in simultaneously cleansing and softening textiles in a laundering process without yellowing consisting essentially of about 1 to 20 parts by weight of a detergent selected from the group consisting of anionic and nonionic detergent, about 1 to 5 parts by weight of a partially alkylated polyethyleneimine polymer of molecular weight of 1,000 to 100,000 as the softening agent, the degree of alkylation of said polymer ranging from 5 to 50 percent and the alkyl moiety ranging from C to C and about I to parts by weight per part of said detergent of a water soluble builder salt selected from the group consisting of inorganic condensed phosphates, inorganic silicates, inorganic borates, inorganic carbonates, nitrilotriacetates, ethylene diamine terraacetates, methylene diphosphonates, citrates, glycollates, and methyl vinyl ether-maleic anhydride interpolymers, the cation of said salt being selected from the group consisting of sodium and potassium.

2. A composition as defined in claim 1 wherein the ratio of detergent to polymer ranges from 10:1 to 1:2 and the range of 5. A composition in accordance with claim 3, wherein the softening agent is a polymer of molecular weight 40,000 60,000 containing 0.2 equivalents of octadecyl group per monomer unit.

6. A process for laundering and softening textiles in a single operation which comprises laundering said textile material with the composition of claim 1 in an aqueous medium. 

2. A composition as defined in claim 1 wherein the ratio of detergent to polymer ranges from 10:1 to 1:2 and the range of builder salt is from 5 to 50 parts by weight per part of detergent.
 3. A composition in accordance with claim 1, wherein the alkyl group is octadecyl.
 4. A composition in accordance with claim 3, wherein the softening agent is a polymer of molecular weight 40,000 - 60,000 containing 0.3 equivalents of octadecyl group per monomer unit.
 5. A composition in accordance with claim 3, wherein the softening agent is a polymer of molecular weight 40,000 - 60,000 containing 0.2 equivalents of octadecyl group per monomEr unit.
 6. A process for laundering and softening textiles in a single operation which comprises laundering said textile material with the composition of claim 1 in an aqueous medium. 